Patent GB-469319-A (GB)
Title: Manufacture of polymerisation products
IPC: C08F2/30
Filed: 1936-01-18
Abstract: Unsaturated organic compounds are polymerized in aqueous emulsion (maintained if necessary by stirring, shaking, passage of gases, or boiling) containing as emulsifying agent an ester, ether or acetal of polyvinyl alcohol, such agent being wholly or partially soluble in water.  There may be polymerized vinyl esters; acrylic, methacrylic, and itaconic acid and their derivatives; styrene; butadiene; chloroprene; mixtures, e.g. vinyl acetate and vinyl chloride, methyl acrylate and vinyl acetate, vinyl esters and chloroprene; partial polymers.  There may be used as emulsifying agents partial polyvinyl ethers or partially saponified esters, ethers, or acetals of polyvinyl alcohol, e.g. a partial saponification product of the polymer obtained by polymerizing a vinyl ester in the presence of aldehyde or drying oil.  There may be added (1) to the emulsion, to the substance to be polymerized, or to both, salts, organic substances such as alcohols e.g. glycerol and glycols, ketones, aldehydes e.g. glyoxal, phenols, esters, hydrocarbons or chlorinated hydrocarbons, sugars, or tanning agents; oils; solids, e.g. kaolin, ground slate, magnesia, whiting; or water-repellent substances, e.g. natural or synthetic resins, high-melting paraffins, fatty acids, waxes; (2) to the unsaturated compounds: preformed polymers, e.g. polyvinyl acetate or polyacrylic acid ester; cellulose derivatives; condensation products of aldehydes with phenols or ureas or of polybasic acids with alcohols or glycols; drying oils or the polymerized constituents contained or produced therein; (3) to the substance to be polymerized, to the product, or to both: softening agents, dyestuffs, pigments, resin, waxes, or fillers, e.g. asbestos, cellulose or wool.  The polymerization may be carried out by heating, illumination or other radiation, or by a combination thereof in presence or absence of a catalyst, under ordinary, increased, or reduced pressure; and preferably the quantity of substance to be polymerized exceeds that of the aqueous liquid in which it is emulsified.  In an example, acrylic nitrile is polymerized in emulsion in an aqueous solution of polyvinyl ethyl ether, methyl cellulose and hydrogen peroxide.  Samples have been furnished under Sect. 2 (5) as follows: (i) vinyl chloride is polymerized in emulsion in an aqueous solution of partially saponified polyvinyl acetate, in the presence of benzoyl peroxide at 100 DEG  C. to give a product soluble in usual solvents; (ii) vinyl chloride is polymerized as in sample (i) but at room temperature to give a product compatible with chloro-toluene and chlorbenzene; (iii) vinyl acetate and linseed stand oil are polymerized in emulsion in an aqueous ammoniacal solution of partially saponified polyvinyl acetate in the presence of benzoyl peroxide; (iv) linseed stand oil is polymerized in emulsion in an aqueous solution of partially saponified polyvinyl acetate in the presence of benzoyl peroxide and cobalt naphthenate; (v), (vi) vinyl acetate is polymerized in emulsion in an aqueous solution of hydrogen peroxide and (v) a partial polyvinyl benzyl ether, (vi) a partial polyvinyl acetate-formal. Specification 367,102 is referred to.  The Specification as open to inspection under Sect. 91 states that the emulsifying agent is one which has no saponifying action, and specifies methyl cellulose, polyvinyl alcohol, phenolaldehyde and urea aldehyde condensates soluble or colloidably soluble in water, sterols, e.g. cholesterol and phytosterol, saponins, inorganic salts having suitable solubility such as aluminium acetate, pectins, gelatines, degradation products of starch, or mixtures thereof.  It includes examples in which vinyl acetate is polymerized in emulsion in an aqueous solution of methyl cellulose, in the presence or absence of benzoyl peroxide.  This subject-matter does not appear in the Specification as accepted.ALSO:Unsaturated organic compounds are polymerized in aqueous emulsion (maintained if necessary by stirring, shaking, passage of gases, or boiling) containing as emulsifying agent an ester, ether or acetal of polyvinyl alcohol, such agent being wholly or partially soluble in water.  There may be polymerized vinyl esters; acrylic, methacrylic, and itaconic acid and their derivatives; styrene; butadiene; chloroprene; mixtures, e.g. vinyl acetate and vinyl chloride, methyl acrylate and vinyl acetate, vinyl esters and chloroprene; partial polymers.  There may be used as emulsifying agents partial polyvinyl ethers or partially saponified esters, ethers, or acetals of polyvinyl alcohol, e.g. a partial saponification product of the polymer obtained by polymerizing a vinyl ester in the presence of aldehyde or drying oil.  There may be added (1) to the emulsion, to the substance to be polymerized, or to both: salts, organic substances such as alcohols, e.g. glycerol and glycols, ketones, aldehydes, e.g. glyoxal, phenols, esters, hydrocarbons or chlorinated hydrocarbons, sugars, or tanning agents; oils; solids, e.g. kaolin, ground slate, magnesia, whiting; or water-repellent substances, e.g. natural or synthetic resins, high-melting paraffins, fatty acids, waxes; (2) to the unsaturated compounds: pre-formed polymers, e.g. polyvinyl acetate or polyacrylic acid ester; cellulose derivatives; condensation products of aldehydes with phenols or ureas or of polybasic acids with alcohols or glycols; drying oils or the polymerized constituents contained or produced therein; (3) to the substance to be polymerized, to the product, or to both: softening agents, dyestuffs, pigments, resin, waxes, or fillers, e.g. asbestos, cellulose or wool.  The polymerization may be carried out by heating, illumination or other radiation, or by a combination thereof in presence or absence of a catalyst, under ordinary, increased, or reduced pressure; and preferably the quantity of substance to be polymerized exceeds that of the aqueous liquid in which it is emulsified.  In an example, acrylic nitrile is polymerized in emulsion in an aqueous solution of polyvinyl ethyl ether, methyl cellulose and hydrogen peroxide.  Samples have been furnished under Sect. 2 (5) as follows: (i) vinyl chloride is polymerized in emulsion in an aqueous solution of partially saponified polyvinyl acetate, in the presence of benzoyl peroxide at 100 DEG  C. to give a product soluble in usual solvents; (ii) vinyl chloride is polymerized as in sample (i) but at room temperature to give a product compatible with chloro-toluene and chlorbenzene; (iii) vinyl acetate and linseed stand oil are polymerized in emulsion in an aqueous ammoniacal solution of partially saponified polyvinyl acetate in the presence p  of benzoyl peroxide; (iv) linseed stand oil is polymerized in emulsion in an aqueous solution of partially saponified polyvinyl acetate in the presence of benzoyl peroxide and cobalt naphthenate; (v), (vi) vinyl acetate is polymerized in emulsion in an aqueous solution of hydrogen peroxide and (v) a partial polyvinyl benzyl ether, (vi) a partial polyvinyl acetate-formal. Specification 367,102 is referred to.  The Specification as open to inspection under Sect. 91 states that the emulsifying agent is one which has no saponifying action, and specifies methyl cellulose, polyvinyl alcohol, phenolaldehyde and urea aldehyde condensates soluble or colloidably soluble in water, sterols, e.g. cholesterol and phytosterol, saponins, inorganic salts having suitable solubility such as aluminium acetate, pectins, gelatines, degradation products of starch, or mixtures thereof.  It includes examples in which vinyl acetate is polymerized in emulsion in an aqueous solution of methyl cellulose, in the presence or absence of benzoyl peroxide.  This subject-matter does not appear in the Specification as accepted.